Perfume compositions

ABSTRACT

NOVEL PERFUME COMPOSITIONS AND PERFUMED ARTICLES ARE DESCRIBED CONTAINING CERTAIN MONOALKYL-3-CHLORO RINGSUBSTITUTED RESORCRCLIC ACIDS ESTERS WHICH IMPART TO THESE PERFUME COMPOSITIONS AND PERFUMED ARTICLES A NATURAL AND DISTINCTLY OAKMOSS NOTE WITHOUT CAUSING DISCOLORATION.

United States Patent ABSTRACT OF THE DISCLOSURE Novel perfume compositions and perfumed articles are described containing certain monoalkyl-B-chloro ring- 3,729,430 Patented Apr. 24, 1973 July 30, 1970 and involves the production of a hydroresorcylic acid ester having the structure:

I OH Cl wherein the R groups represent alkyl.

substituted resorcylic acid esters which impart to these perfume compositions and perfumed articles a natural and distinctly oakmoss note without causing discoloration.

This application is a continuation-in-part of copending application for U.S. Ser. No. 113,699 filed on 'Feb. 3,

119711, now U.S. 3,701,801.

BACKGROUND OF THE INVENTION Natural oakmoss is commercially important in producing high-grade fragrance compositions. Oakmoss constitutes an important and basic part of the fragrance impression of chypre and lavender. In view of the limited availability of natural oakmoss synthetic substitutes are desirable and have been long sought.

It has been found that certain alkyl ring-substituted resorcylic acid esters simulate and resemble the fragrance impression of oakmoss. While a number of routes for the production of such resorcylic acid esters are available, they are rather tedious, complicated, generally uneco- THE INVENTION The invention is thus related to alkyl 3-chloro ring-substituted resorcylic acid esters, their mode of preparation. and their use as fragrance materials.

The novel 3-chloro ring-substituted resorcylic acid esters of this invention may be represented by the following formula:

wherein R and either R or R is a lower alkyl radical containing from 1 to 5 carbon atoms, the other of R or R 7 being hydrogen. Representative of the compounds included nomic and none have been shown to produce alkyl 3- chloro ring-substituted resorcylic acid esters. For instance, one of these methods, as reported by Sonn in Berichte, 62'B B, 3012-6 (1929), involves utilization of the rather expensive, and difficultly recoverable, palladium catalyst for the aromatization of monoor dialkyl ringsubstituted hydro alkyl resorcylates. Another method shown by Robertson et al. in I. Am. Chem. Soc., pp. 313- 20 (1930) involves a multi-step sequence diflicult to perform and tedious to carry out.

Still another method disclosed by Neelakantan et al., Indian J. Chem, 2(12), 478-84 shows the chlorination of methyl 6-methylresorcylate to yield methyl 6-methyl-3,5- dichlororesorcylate. However, Neelakantan et al. did not show production of the alkyl 3-chloro ring-substituted resorcyclic acid esters with only one chlorine atom substituted at the 3 position on the benzene ring.

In Canadian Pat. 837,131 issued on Mar. 7, 1970 monoand dialkyl ring-substituted resorcylic acid esters are shown to be produced by reacting the corresponding dihydroresorcylic acid esters with an oxidative chlorine material. No temperature limitations are set forth therein. The dihydroresorcylie acid esters are prepared by treating B-ketoalkanoic acid esters with a,/8-unsaturated alkyl alkenoates in the presence of an alkali metal alcoholate. The synthesis as set forth therein is not shown to yield alkyl monochloro ring-substituted resorcylic acid esters.

A process for producing non-aromatized materials having a halogen moiety substituted on the ring is shown by Teitel in German Oifenlegenschrift 2,002,815 published within said formula are:

methyl 6-methyl-3-chlororesorcylate methyl 6-isopropyl-3-chlororesorcylate methyl 6-ethyl-3-ch1ororesorcylate methyl 6-n-butyl-3-chlororesorcylate methyl 6-n-propyl-3-chlororesorcylate methyl 6-isobutyl-3-chlororesorcylate ethyl 6-rnethyl-3-chlororesorcylate ethyl 6-isopropyl-3-chlororesorcylate ethyl 6-ethyl-3-chlororesorcylate ethyl-6-n-butyl-3-chlororeorcylate ethyl 6-n-propyl3-chlororesorcylate ethyl 6-isobutyl-3-chlororesorcylate n-propyl 6-methyl-3-chlororesorcylate n-propyl 6-isopropyl-3-chlororesorcylate n-propyl 6-ethyl-3-chlororesorcylate n-propyl 6-n-butyl-3-chlororesorcylate n-propyl 6-n-propyl-3-ch1ororesorcylate n-propyl 6-isobutyl-3-chlororesorcylate i-butyl 6-methy1-3-chlororesorcylate i-butyl 6-isopropyl-3-chlororesorcylate i-butyl 6-ethyl-3-chlororesorcylate i-butyl 6-n butyl-3-chlororesorcylate i-butyl 6-n-propyl-3-chlororesorcylate i-butyl 6-isobutyl-3-chlororesorcylate methyl 5-methy13-chlororesorcylate methyl 5-isopropyl-3-chlororesorcylate methyl 5-ethyl-3-chlor0resorcylate methyl 5-n-butyl-3-chlororesorcylate methyl 5-n-propyl-3-chlororesorcylate methyl 5-isobutyl-3-chlororesorcylate ethyl 5methyl-3-chlororesorcylate ethyl 5-isopropyl-3-chlororesorcylate ethyl 5-ethy1-3-chlororesorcylate 3 ethyl -n-butyl-3-chlororesorcylateethyl 5-n-propyl-3-chlororesorcylate ethyl S-isobutyl-3-chlororesorcylate n-propyl 5-methyl-3-chlororesorcylate n-propyl 5-isopropyl-3-chlororesorcylate n-propyl 5-ethyl-3-chlororesorcylate n-propyl 5-nbutyl-3-chlororesorcylate n-propyl 5-npropyl-3-chlorores0rcylate n-propyl 5-isobutyl-3-chlororesorcylate i-butyl 5-methyl-3-chlororesorcylate i-butyl 5-isopropyl-3-chlororesorcylate i-butyl 5-ethyl-3-chlororesorcylate i-butyl 5-n-butyl-3chl'ororesorcylate i-butyl 5-n-propyl-3-chlororesorcylate i-butyl 5-isobutyl-3-chlororesorcylate.

The resorcylic acid esters of this invention effectively simulate and resemble oakmoss fragrance and are suitable for use by themselves as fragrance materials or in combination with other ingredients in a perfume composition such as a hypre or lavender perfume. The C-1 and C-2. lower alkyl resorcylic esters are preferred as fragrance materials and the methyl esters are most suitable. Particularly preferred is methyl 6-methyl-3-chlororesorcylate by reason of its pronounced and long lasting mousse-like odor.

Also, in accordance with this invention it has been found that monoalkyl 3-chloro ring-substituted resorcylic acid esters thereof, as represented by the formula wherein R and either of R or R is a lower alkyl radical containing from 1 to 5 carbon atoms (and the other of R or R is hydrogen) can be conveniently and more economically prepared by reacting a mono-ring-substituted dihydroresorcylate ester with an oxidative chlorine material. This process has been found to result in high yields of the products desired and suppresses undesirable side reactions.

Suitable mono-ring-substituted dihydroresorcylic acid esters for this reaction may be represented by the following formulae:

wherein R and either of R or R is a lower alkyl radical containing from 1 to 5 carbon atoms including methyl, ethyl, propyl, butyl, isopropyl and amyl. Mixtures of such isomers can be used. The particular starting material selected will depend upon the end product desired and appropriate choices will be readily apparent. The dihydroresorcylate starting material is preferably substantially pure so as to avoid undesirable side reactions and facilitate isolation and recovery of the end product. Such dihydroresorcylic acid ester starting materials may be prepared by any of the known techniques. For example, such 4 dihydroresorcylic acid esters can be readily made by reacting a beta-keto alkanoic acid ester of the formula in the presence of an alkali metal alcoholate such as sodium methylate. In the above formulae R and R are each lower alkyl and either of R or R is lower alkyl, the other being hydrogen. A further description of the preparation of the intermediate dihydroresorcylic acid esters .may 'be found in Sonn, Berichte, 62B, 3012-6 (1929).

The oxidative chlorine material may be molecular chlorine or'any material which, under the conditions of the reaction, yields or is a source of oxidative chlorine such as hypochlorous acid, sulfuryl chloride or nitrosyl chloride. Chlorine is preferred.

The yield obtained when practicing the process of this invention is affected by the degree of contact of the reactants. Thus, if the contact time of the oxidative chlorine material with the hydroresorcylic acid ester is too low, the yields are lower and large amounts of unreacted hydroresorcylic acid ester remains unconverted and must be separated from the reaction mixture. Inter mixing of the reactants as by agitation or turbulent mixing will increase the contact time and increase the yield of desired product.

When hypochlorous acid is employed a two phase aqueous-non-aqueous reaction system results where the degree of contact between the two phases is an important if not controlling factor in determining the yield of product. The degree of contact is modified or regulated by nature of the agitation or intermixing.

It is generally desirable to carry out the reaction in an inert solvent vehicle for the hydroresorcylate since at the reaction temperatures required (from --20 to +50 C. or those usually preferred, i.e., from about l025 C.) the reactant is in solid form. Such a solvent medium, therefore, is useful to effect adequate contact between the reactants. Suitable inert reaction solvents include non-reactive halogenated hydrocarbons such as chloroform and tetrachloroethane and non-reactive alkanoic acids such as acetic and propionic acids.

The reaction conditions of temperature and pressure are critical and will depend upon a variety of factors including the time of the reaction, the particular reactants used, and the products desired. Generally, it is expedient to run the reaction at atmospheric pressure although elevated pressures may be employed. The reaction must be conducted in the range from about -20 to +50 C. and preferably in the range of from about 10- 25 C. The time of reaction is generally determined by the temperature of the reaction and by the absolute pressure above the reaction mass. Other factors such as the nature of the reactants, the extent and duration of contact of the reactants, the mixing system utilized, and the yield and conversions desired may also affect the reaction time. It is usually preferred to carry out the reaction for a period of time from about one to ten hours since shorter periods adversely affect yields while longer periods give no further advantage in the process.

The process is suitably carried out by dissolving or suspending the hydro-resorcylic acid ester in an inert organic vehicle such as chloroform or acetic acid whereby a two phase slurry of solid and saturated solution is formed. The oxidative chlorine material, as for example chlorine gas, is introduced into the reaction system, as by bubbling it through the reaction mass, while vigorously agitating the reaction system to achieve intimate intermixing. The organic solvent or vehicle is then removed from the reaction mass, the reactants separated .and the reaction product may be recovered and isolated by any conventional technique such as selective extraction, crystallization or the like.

The monoalkyl-3-chlororesorcylic acid esters obtained by practicing the process of this invention are novel and are useful fragrance materials. Used individually or in admixture with one another, the monoalkyl-3-chloro resorcylic acid esters of this invention have pronounced oakmoss fragrances and are suitable for use as fragrance materials themselves or as components of fragrance compositions or of perfume compositions. Thus, materials produced by the process of this invention are useful as olfactory agents and fragrances.

The term perfume composition is used herein to mean a mixture of compounds, including perfume adjuvants, for example natural perfume oils, synthetic perfume oils, alcohols, aldehydes, ketones, esters, lactones, ethers, anthranilates, acetals, ketals, oximes, carboxylic acids, aromatic hydroxy compounds, diphenyl compounds, azoles, quinolines, terpenes, the macrocyclic musks including ketones, and polycyclic musks including Tetralin musks; and in addition, frequently hydrocarbons which are admixed so that the combined odors of the individual components produce a pleasant and desired fragrance. These additional adjuvants are specifically illustrated in the examples set forth below. Such perfume compositions usually contain: (a) the main note (the bouquet or foundation-stone) of the composition; (b) modifiers which round off and accompany the main note; fixatives including odorous substances which lend a particular note to the perfume throughout all stages of evaporation and substances which retard evaporation; and (d) top-notes which are usually low-boiling fresh-smelling materials. Such perfume compositions or the novel monoal-kyl-3-chloro-resorcylic acid esters of this invention can be used in conjunction with carriers, vehicles, solvents, dispersants, emulsifiers, surface-active agents, aerosol propellants, fixatives, and the like.

In perfume compositions the individual components contribute their particular olfactory characteristics, but the overall effect of the perfume composition can be more than the sum of the effect of each ingredient. Thus, the individual compounds of this invention, or mixtures thereof, may be used to alter the aroma characteristics of a perfume composition, for example, by high-lighting or moderating the olfactory contribution of another ingredient of the composition.

The amounts of the resorcylic acid ester of this invention which will be effective in perfume compositions depends upon several factors, including the other ingredients of the composition, their amounts and the particular effects which are desired. It has been found that perfume compositions containing as little as 0.5% by weight of the compound of the invention, or even less, can be used to impart a basic oakrnoss note to such materials as crepe de chene, lavender, or chypre for use in soaps, cosmetics, lotions, handkerchief perfumes and similar products. The amount employed will depend on considerations of cost, nature of the end product, the effect desired on the finished product and the particular fragrance sought.

The compositions of matter disclosed herein can be used alone, in a fragrance-modifying composition, or in a perfume composition as olfactory components in detergents and soaps; space deodorants; perfumes; colognes; bath preparations such as bath oil and bath salts; hair preparations such as lacquers, brillantines, pomades, and shampoos; cosmetic preparations such as creams, deodorants, hand lotions, and sun screens; powders such as talcs, dusting powders, and face powders; and the like.

The following examples serve to illustrate embodiments of the invention as it is now preferred to practice it. It

will be understood that these examples are illustrative and the invention is to be considered restricted thereto only as indicated in the appended claims.

EXAMPLE I Methyl 6-methyl-3-chlororesorcylate Into a slurry of 184 gms. (1 mole) of methyl dihydro-6- methylresorcylate in 500 cc. of glacial acetic acid is bubbled 140 grns. (2 moles) of chlorine gas at a tem-- perature of 15 C. When the addition is complete, the mixture is stirred for /2 hour and then heated to 50 until evolution of the HCl gas ceases. The solution is cooled and poured into water. The precipitate is filtered, Washed with water, 5% aqueous sodium bicarbonate solution, and finally with water. The solid is dried in vacuum yielding 146.4 gms. (68%) of methyl 6-methyl-3-chlororesorcylate, M.P. 13940; ms., 184, 186, 216 (m.), 218 (m|2), 65; NM-R, 6, 2.42 (s., 3H), 3.79 (s., 3H), 6.41 (s., 3H).

The product is a White crystalline material having a mousse-like odor which can be imparted to soap at a level of 0.25%.

EXAMPLE II Perfume composition The following mixture is prepared:

Ingredient Grams Jasmine liquid, A 15 Rose liquid 5 Solution orris 6 Santal oil E.I 6 Berga-mot Patchouli oil 6 Musk ketone, /s in BB 60 Vetivert oil 5 Methyl 6-methyl 3 chlororesorcylate (produced by the process of Example I) [tincture /5] 200 Coumarin 2 Vanilin 1.5 Heliotropin 2 Rose synthetic 25 'Rose otto, Bulgarian 10 Pimento oil 5 Olibanum resinoid 10 Bitter orange oil 4 Ambrette seed oil 2 Musk tincture, 3 percent 250 Alcohol 4000 The foregoing perfume formulation is an important part of chypre essence. The methyl 6-methy1-3-chlororesorcylate is used as a replacement for oakmoss. This perfume is incorporated into a handkerchief perfume at the 0.1% by Weight level. The methyl 6-methyl-3-chlororesorcylate gives to this fragrance a natural and distinctly oakmoss note.

EXAMPLE III Methyl G-methyl-3-chlororesorcylate Into a 5 liter flask equipped with stirrer, thermometer, condenser, gas inlet tube and bub'bler are placed the following materials:

3.5 liters of chloroform 421 grams of methyl 6-methyldihydroresorcylate.

Chlorine gas is added while stirring the reaction mass over a period of one hour until the chlorine is no longer taken up and the reaction mass becomes clear. During the bubbling the reaction mass temperature increases from 22 C. to 37 C. At the end of the reaction, the hydrogen chloride gas ceases to evolve. The solid material is recovered by filtration and weighs 507.1 grams. It is dissolved in 2 liters diethyl ether. The diethyl ether solution is washed using sodium bicarbonate washes until CO no longer evolves in the wash solution. The bicarbonate solutions are extracted with ether and the ether layers combined and washed with 10 volumes of sodium hydroxide at C. The methyl 6-methylchlororesorcylate product is recovered by crystallization from the ether layers. 111 grams of dried product is obtained. The structure of the product is shown to be methyl 6-methyl-3-chlororesorcylate by IR, NMR and mass spectral analysis. The product is a white crystalline material having a melting point of 135.8l37.8 C. This material has a mousse-like odor Methyl 6 methyl 3-chlororesorcylate (produced by the process of Example III) 50 Musk xylene 50 Styrax resin 100 The foregoing perfume formulation is an important part of chypre essence. The methyl 6-methyl-3-chlororesorcylate is used as a replacement for oakmoss. This perfume is incorporated into a soap perfume at the 0.1% level. The methyl 6-methyl-3-chlororesorcylate gives to this fragrance a natural and distinctly oakmoss note.

EXAMPLE V Ethyl 6-ethyl-3-chlororesorcylate Into a 5 liter flask equipped with stirrer, thermometer, and condenser gas inlet tube and bubbler are placed the following materals:

35. liters of chloroform 405 grams of ethyl 6-ethyldihydroresorcylate.

Chlorine gas is added while stirring the reaction mass over a period of one hour until the chlorine is no longer taken up and the reaction mass becomes clear. During the bubbling the reaction mass temperature increases from 22 C. up to 42 C. At the end of the reaction, the hydrogen chloride gas ceases to evolve. The solid material is recovered by filtration and Weighs 450 grams. It is dissolved in 2 liters of diethyl ether. The diethyl ether solution is Washed using sodium bicarbonate washes until CO no longer evolves in the wash solution. The bicarbonate solutions are extracted with ether and the ether layers combined and washed with 10 volumes of sodium hydroxide at 5 C. The ethyl 6-ethyl-3-chlororesorcylate product is recovered by crystallization from the ether layers. 150 grams of dried product is obtained. The structure of the product is shown to be ethyl 6-ethyl-3-chlo-roresorcylate by IR, NMR and mass spectral analysis. The product is a white crystalline material. This material has a mousse-like odor which can be imparted to soap at a level of 8 EXAMPLE VI Perfume composition The following mixture is prepared:

The foregoing perfume formulation is an important part of chypre essence. The ethyl 6-ethyl-3-chlororesorcylate is used as a replacement for oakmoss. This perfume is incorporated into a soap perfume at the 0.1% level. The ethyl 6-ethyl-3-chlororesorcylate gives to this fragrance a natural and distinctly oakmoss note.

EXAMPLE VII Ethyl 6methyl-3-chlororesorcylate Into a 5 liter flask equipped with stirrer, thermometer, condenser, gas inlet tube and bubbler are placed the following materials:

750 cc. of glacial acetic acid 297 grams of ethyl -6-methyldihydroresorcylate. Chlorine gas is added while stirring the reaction mass over a period of one hour until the chlorine is no longer taken up and the reaction mass becomes clear. During the bubbling the reaction mass temperature increases from- 17 C. to 22 C. The slurry is then heated to reflux until hydrogen chloride ceases to be evolved. The reaction mass is then added to one liter of water and the solid precipitate is filtered. The product is then crystallized from a 75% solution of acetic acid yielding 111 grams of dried product. The product is shown to be ethyl 6- methyl-3-chlororesorcylate by IR, NMR and mass spectral analysis. The product has melting point of 150 to 151 C. This material has a mousse-like odor which can be imparted to soap at a level of 1%.

EXAMPLE V111 Perfume composition The following mixture is prepared:

Ingredient- Grams Jasmin liquid, A 15 Rose liquid 5 Solution orris 6 Santal oil E-I. 6 Bergamot Patchouli oil 6 Musk ketone, /s in BB 60 Vetivert oil 5 Ethyl 6-methyl-3-chlororesorcylate (produced by the process of Example VII) [tincture The foregoing perfume formulation is an important part of chypre essence. The ethyl 6-methyl-3-chlororesorcylate is used as a replacement for oakmoss. This perfume is incorporated into a handkerchief perfume at the 0.2% by weight level. The ethyl 6-methyl-3-chlororesorcylate gives to this fragrance a natural and distinctly oakmoss note.

EXAMPLE IX Methyl 6-methyl-3-chlororesorcylate Into a two-liter flask equipped with stirrer, thermometer, condenser and gas inlet tube are added the following ingredients:

500 n11. propionic acid 92 gms. methyl G-methyldihydroresorcylate.

While maintaining the reaction mass at 15 C., 35 gms. of chlorine gas is added over a period of /2 hour. The reaction mass is then heated to 60 C. and maintained at that temperature for a period of /2 hour. As the reaction mass clears, a precipitate is formed which precipitate is separated by means of filtration. The product of reaction is found to be a mixture of 2 compounds:

(1) Methyl 6-methyl-3-chlororesorcylate; and (2) 1 methyl-3,S-dihydroxy-4-chlorobenzene (2-chloroorcinol),

the structures of which are confirmed by NMR, GLC and mass spectral analysis. The materials are separated by means of fractional crystallization.

The desired product has an excellent mousse aroma.

EXAMPLE X Methyl 5-methyl-3-chlororesorcylate Into a slurry of 184 gms. (1 mole) of methyl dihydro- S-methylresorcylate in 500 cc. of glacial acetic acid is bubbled 140 gms. (2 moles) of chlorine gas at a temperature of C. When the addition is complete, the mixture is stirred for 40 minutes and then heated to 60 C. until evolution of the HCl gas ceases. The solution is cooled and poured into water. The precipitate is filtered, washed with water, 5% aqueous sodium, bicarbonate solution, and finally with water. The solid is dried in vacuum yielding 155 gms. of methyl 3-chloro-S-methylresorcylate, confirmed by IR, NMR and mass spectral analysis.

The product has a mousse-like odor which can be imparted to soap at a level of 1.50%.

The foregoing perfume formulation is an important part of chypre essence. The methyl 5-methyl-3-chlororesorcylate is used as a replacement for oakmoss. This 1 0 perfume is incorporated into a soap perfume at the 0.2% level. The methyl 5-methyl-3-chlororesorcylate gives to this fragrance a natural and distinctly oakmoss note.

EXAMPLE XII The following mixture is prepared:

Parts by Ingredientsweight Coumarin l5 6 oxa-l,l,2,3,3,8-hexamethyl-2,3,5,6,7,8-hexahydro-1H-benz(f)-indene (50% solution in diethyl phthalate) 60 Vanillin 2.5 Myrrh coeur (50% solution in diethyl phthalate) 5 Olibanum coeur (50% solution in diethyl phthalate) 5 a-Isomethyl ionone 30 Civet tincture (10% solution in ethyl alcohol) 10 Jasmin absolute/Chassis 40 Eugenol 10 Isoeugenol 10 Rose oil, Moroccan 50 4 (4-hydroxy-4-methylpentyl)-3-cyclohexane- 10-carboxaldehyde 15 Castoreum tincture (20% solution in ethyl alcohol) 6 Styrallyl acetate 7.5 Ylang extra 5 n-Heptaldehyde, dirnethylacetal (10% solution in diethyl phthalate) 10 1-hydIoxy-4-t-butyl cyclohexane acetate 20 IO-undecenyl aldehyde (10% solution in diethyl phthalate) 3 3a-ethyl-dodecahydra-6,6,9a trimethyl naphthol-(2,1,b)furan 15 l,1,2,3,3 pentamethyl 6,7 dihydro-5(4H)- indanone 5 8,9'-epoxycedrane 50 Opopanax oil 0.25 Geraniol coeur 1.25 Neroli oil 1.25 Lemon terpeneless 2.5 Rosemary French 2.5 Lavandin 2.5 Benzoin coeur 2.5 Tetrahydro muguol (ref. p. 2918Perfume & Flavor Chemicals, S. Arctander II, (1969) 3.75 Linalyl acetate (Hofiman La Roche) 3.75 Z-t-butyl cyclohexanol acetate 7.5 Petitgrain oil 15 Orange oil Florida 22.5 Lemon oil California 27.5

Bergamot oil 50 'Piperonyl acetate 1.5 3-chloro-6-methyl resorcylic acid methyl ester (50% solution in diethyl phthalate) 30 The 3-chloro- 6-methyl resorcylic acid methyl ester, at

the level given, imparts to the mixture a distinct oakmoss note. The 3-chloro-6-methyl resorcylic acid methyl ester acts as a replacement for natural oakmoss without the disadvantage of discoloration that is caused by use of the natural oakmoss in such crepe de chene formulations. This crepe de chene perfume formulation is incorporated in a standard soap base at a level of 1% thus imparting the crepe de chene fragrance to the soap without causing discoloration.

1 1 What is claimed is: 1.'A perfume composition comprising a monoalkyl-3- chloro-resorcylic acid ester having the formula HO OH wherein R is lower alkyl and either of R or R is a lower alkyl radical containing from 1-5 carbon atoms and the other of R or R is hydrogen and at least one perfume adjuvant, said monoalkyl-3-chloro-resorcylic acid ester being present in amounts sufficient to alter the fragrance of said adjuvant.

2. The composition of claim 1, wherein each of R and R is methyl and R is hydrogen.

3. The composition of claim 1, wherein R is methyl,

R is ethyl and R is hydrogen.

1 2 References Cited FOREIGN PATENTS 3/1970 Canada. 2/1970 Belgium.

OTHER REFERENCES ALBERT T. MYERS, Primary Examiner A. P. FAGELSON, Assistant Examiner US. 01. X.R. 

